Systemic fungicides



United States Patent Office 3,086,913 Patented Apr. 23, 1963 3,086,913 SYSTEMIC FUNGICIDES James M. Hamilton, 574 S. Main St., and Michael Szkolnik, RD. 2, both of Geneva, N.Y., and Ernest Sondheimer, Geneva, N.Y. (956 Westmoreland Ave., Syracuse 10, N.Y.)

No Drawing. Continuation of application Ser. No. 615,752, Oct. 15, 1956. This application Apr. 27, 1962, Ser. No. 190,767

6 Claims. (Cl. 167-65) This invention relates to novel compositions of matter and to a novel process and is particularly directed to novel compositions and a novel process for the controlling of plant diseases.

Cycloheximide is an antibiotic substance produced as an elaboration product of Streptomyces griseus according to the procedures set forth in US. Patents 2,574,519 and 2,612,502; by Leach et al. in J. Am. Chem. Soc. 69, 474 (1947); and by Ford et al. in J. Am. Chem. Soc. 70, 1223-1225 (1948). Cycloheximide has been found to be an effective fungicide and to be particularly useful in the control of plant diseases.

It is known that when cycloheximide is reacted with acetic anhydride, the acetate, melting point 148149 degrees centigrade, is obtained. This compound has heretofore been thought to be biologically inactive. See Ford et al. and Leach et al. supra. Although Leach et all report a diacetate, it was subsequently found that cycloheximide contains only one hydroxyl group and that the acetate was really the monoacetate. See Ford et al., supra, and Kornfeld et al., I. Am. Chem. Soc. 71, 150 159 (1949). Various other known derivatives of cycloheximide also have been considered to be inactive or to have little value when compared with cycloheximide.

It has now been found that certain derivatives of cyclehexirnide are effective for the control of plant fungal diseases, and that quite surprisingly the compounds are translocated so that new foliage growth is protected as well as the treated foliage. This is surprising because cycloheximide is not translocated. It is a surface protectant and also acts to eradicate established infections in the treated foliage.

The derivatives of cycloheximide which have been found to be effective are the carboxylic acid esters, particularly the lower alkanoic acid esters, such as the acetate, and the derivatives which are formed by reaction with the keto group of cycloheximide, such as the oxime. the semicarbazone, dehydrocycloheximide, anhydrocycloheximide, and cycloheximide isomer.

In carrying out the invention, the active material oxime advantageously is dissolved in water and the water solution sprayed on foliage of plants which it is desired to protect from fungal attack. Thus the concentration of the active material in the solution may range from around one to around 100 parts per million, or up to the solubility of the active material in water. Such solutions advantageously are prepared by dissolving the active material in a water-miscible solvent such as dimethyl-formamide, acetone, methanol, or ethanol and adding the resulting solution to the spray tank with proper stirring and agitation. By the use of such concentrated solutions in which the active material suitably can range from about one to about 25 percent or more depending upon the solubility in the solvent, the very dilute aqueous solutions which are advantageously employed according to the invention are readily prepared. A concentrate containing one percent of the active material in ethanol provides a composition which for each level teaspoon cc.) per gallon give about thirteen to fourteen parts of the active material per million parts of water. Each pint per gallons provides about the same concentration. Similarly a 17.5 percent solution in dimethylformamide (or acetone or methanol or ethanol) when diluted provides about thirteen to fourteen parts of the active material for each million parts of water.

Wetting and spreading agents can be included in the spray solutions in accordance with the usual practice in the agricultural art. Anionic, cationic and non-ionic surfactants can be used. Suitable surfactants include alkyl sulfates and sulfonates, alkylarylsulfonates, sulfosuccinate esters, polyoxyethylene sulfates, polyoxyethylene sorbitan monolaurate, alkylarylpolyether sulfates, alkylarylpolyether alcohols, alkylnaphthalene sulfonates, alkyl quaternary ammonium salts, sulfated fatty acid esters, sulfated fatty acid amides, glycerol mannitan laurate, polyalkylether condensates of fatty acids, and ligninsulfonates.

If desired, the active material can be compounded into a wettable powder. Thus the active material can be milled with an inert powder such as talc, pyrophyllite, Georgia clay, bentonite, or mixtures thereof and a wetting and dispersing material to provide a composition which is readily incorporated into a spray solution. A suitable formulation is obtained by milling and blending 434.5 pounds of Georgia clay, 4.5 pounds of Triton X-lOO (an alkylarylpolyether alcohol) as a wetting agent, 9 pounds of Daxad 27 (polymerized sodium salts of substituted benzoic long chain alkyl sulfonic acid) as a dispersant, and 5.5 pounds of the active material. The resulting composition has the following percentage (by weight) composition.

Percent Active material 1.2 Triton X-lOO l Daxad 27 2 Georgia clay 95.8

Table 1 Leaf Spot on New Leares- Treatment Lesions per 2 sq. in.

Oyclohevimide oxime:

CONTROL Unsprayed Gycloheximide: 1 ppm.

Table II gives the comparative incidence of leaf spots on new leaves in lesions per 2 square inches for a number of the active compounds. As in the tests shown in Table 1, young cherry trees were sprayed with aqueous compositions containing the active materials in the concentrations indicated and were inoculated with Coccomyces hiemalis after five days.

3 Table II Treatment: Lesions per 2 sq. in. Unsprayed 69 Cycloheximide oxime, 10 p.p.m 39 Cycloheximide oxime, 60 p.p.m 13 Cycloheximide semicarbazone, 10 p.p.m 2 Cycloheximide isomer, 10 p.p.m 1 Cycloheximide acetate, 10 p.p.m 5 Anhydroheximide, 10 p.p.m 17 Dehydrohexirnide, 10 p.p.m 32

The data given in these tables show that the infection was controlled in the new foliage and therefore that the fungicide was translocated from the old foliage to the new.

It is to be understood that the invention is not to be limited to the exact details of operation or exact compounds shown and described, as obvious modifications and equivalents will be apparent to one skilled in the art, and the invention is therefore to be limited only by the scope of the appended claims.

This application is a continuation of our application Serial No. 615,752, filed October 15, 1956, now abandoned.

We claim:

1. A process for controlling fungal diseases of plants which comprises applying to the plant a compound that translocates systemically in the plant to growth developing after the application of the compound to the plant whereby protection of post-application new growth as well as old growth is obtained, said compound being selected from the group consisting of cycloheximide oxime and cycloheximide semicarbazone.

2. A process as defined in claim 1 wherein the compound is cycloheximide oxime.

3. A process as defined in claim 1 wherein the compound is cycloheximide semicarbazone.

4. A composition for controlling fungus diseases of plants comprising in admixture a compound that on application to a plant translocates systemically in the plant to growth developing after application of the compound to the plant whereby protection of post-application growth is obtained, a surfactant, and a carrier, said compound being selected from the group consisting of cycloheximide oxime and cycloheximide semicarbazone.

5. A composition as defined in claim 4 wherein the compound is cycloheximide oximc.

6. A composition as defined in claim 4 wherein the compound is cycloheximide semicarbazone.

References Cited in the fiie of this patent UNITED STATES PATENTS 2,885,320 Murray -2 May 5, 1959 2,894,872 Murray July 14, 1959 2,903,457 Ford Sept. 8, 1959 2,980,580 Klomparens Apr. 18, 1961. 2,982,687 Klomparens May 2, 1961 2,982,688 Klomparens May 2, 1961 OTHER REFERENCES Hamilton et al.: Systemic Control of Cherry Leaf Spot Fungus by Foliar Sprays of Actidione Derivatives, Science 123, pp. 1175-1176, June 29, 1956.

Hacker et al.: Cycloheximide Analogues Cause Preinfection Resistance to Puccinia grmninis var. tritici in Spring Wheat, Phytopathology 47, p. 14 (1957).

Hacker et al.: Chemically Induced Resistance to Stem Rust of Wheat by Derivatives of Actidione, Plant Disease Reporter 41, pp. 442-446 (1957).

Hacker et al.: Report on 1957 Field Tests of Actidione Derivatives for Control of Black Stern Rust of Wheat, Plant Disease Reporter 42, pp. 609-613 (1958).

Lemin et al.: Degradation of Cycloheximide Derivatives in Plants, Plant Disease Reporter 41, pp. 447-448, 1957 Wallen: Control of Stem Rust of Wheat With Antibiotics II, Systemic Activity and Effectiveness of Derivatives of Cycloheximide, Plant Disease Reporter 42, pp. 363-366 (1958).

Wallen et al.: The Systemic Activity of Cycloheximide in Seedlings, Phytopathology 47, pp. 291-294 (May 1957 Goldberg: Antibiotics, Their Chemistry and Non- Medical Uses," D. Van. Nostrand Co. Inc, pp. 347-348, 362-363 (copyright 1959). 

1. A PROCESS FOR CONTROLLING FUNGAL DISEASES OF PLANTS WHICH COMPRISES APPLUING TO THE PLANT A COMPOUND THAT TRANSLOCATES SYSTEMICALLY IN THE PLANT TO GROWTH DEVELOPING AFTER THE APPLICATION OF THE COMPOUND TO THE PLANT WHEREBY PROTECTION OF POST-APPLICATION NEW GROWTH AS WELL AS OLD GROWTH IS OBTAINED, SAID COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF CUCLOHEXIMIDE OXINE AND CYCLOHEXIMIDE SEMICARBAZONE. 